Compounded lubricating oil



Patented June 9, 1953 CQMEOUNDED LUBRICATING OIL Charl s A, Wc se s me v le, N- ssi nor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application March 16, 1950, Serial No. 150,103

This invention relates to mineral lubricating oils containing an additive which serves to inhibit rusting of metal surfaces and to increase the load carrying characteristics of the lubricant.

A primary object of the present invention is the preparation of compositions which may be employed as internal combustion engine lubricants and which will also serve for the protection of exposed surfaces of such engines when the same are not in use. When operating such engines in climates having a high humidity, rusting begins within a very short period of time after the engine is shut down. The compositions of the present invention are particularly valuable in preventing such rusting and they are valuable not only in internal combustion engines, but with oil bases of suitable viscosity they may be employed as cutting oils or as penetrating oils, lubricants for fire arms, ordnance equipment, industrial machinery, etc, and in fact for any lubricating purposes Where metal surfaces are exposed to moisture.

The new class of additives of the present in-' vention serve not only to inhibit rustin but. also for the purpose of increasing the load bearing properties of the oil to which they are added. These additives may be defined as aliphatic or cycloaliphatic amine salts of pentachlorophenol. They may be formed by contacting pentachlorophenol with an aliphatic amine in equimolecular proportions at ordinary temperatures, but it is usually desirable to heat the mixture to a temperature of the order of 100-12 0 C. to insure completion of the reaction. No catalyst is requ red- The aliphatic or cycloaliphatic amines which may be advantageously reacted with pentachlorophenol to form the additives of this invention should contain a total of at least eight carbon atoms to provide sufficient oil solubility in the resulting salt. The amines may be primary, secondary; or tertiary amines, and'they may contain straight or branched chain, saturatedor unsaturated hydrocarbon groups. There may be present various substituent atoms or groups, such as halogen atoms, nitro groups, hy- 'droxyl groups, alkoxy groups, ester groups, phosphate and thiophosphate groups, and the like, provided only that the amine molecule does not contain a f cid. roupnum f mines vs talde for h pose ay be mentioned nl-octylalnine, learnino-3g5 5-trimethylhexane, n-ldodecylamine, tertedodecylamine, n-hexadeeylamine; n-octadecylamine, din-butylamine tri-n-butylamine, dicyclohexyl- Among the large 8 Claims. (C l. 252-51.5)

2 amine, high molecular weight aliphatic acid esters of triethanolamine such as the tall oil monoester of triethanolamine, and the like, as well as commercial mixtures of primary amines derived from fatty-acids, such as Lorol amine, which is a mixture of C10 to 018 primary amines derived from coconut'oil acids.

The additives of the present invention may be advantageously employed with petroleum fractions of a wide variety, although their preferred use is in lubricating oil bases to form lubricant compositions which also act as corrosion preventives. The base stocks may be derivedirom various types of crude petroleum and may'consist of distillates or blends of various kinds which have been refined by any of the conventional methods. Synthetic oils may also be used such as those obtained by the polymerization ofolefins or by the hydrogenation of coal or its products. An ester type base oil, such as 2-ethylhexyl sebacate, may also be used. In the case of lubricants the base stock chosen will normally be that oil which without the new additives gives the optimum performance in the service contemplated. The base oils may vary considerably in slushing'oils, which may consist of a mixture of naphtha and lubricating oil and maygcontain small amounts of petrolatum or a fatty compound such as degras.

For the purpose of'the present invention the additives described herein are incorporated in the base stock in proportions generally ranging from 0.01% to 10% by weight. In some cases larger-proportions than those specified may be employed to advantage.

The following examples illustrate the application of the present invention to a lubricant suitable for use in an airplane engine, but these 7 examples are not to be construed as limiting the invention in any way.

Example 1' 6.0; g. (0.225 mol) of pentachlorophenol was mixed with 60 g. (0.225 mol) of acommercial gallon.

mixture of primary amines consisting of approximately the following composition:

A mildly exothermic reaction took place. To insure completion of the reaction, the mixture was heated with stirring at a temperature of 120 C. for 30 minutes. The reaction product, obtained in quantitative yield, was a dark viscous liquid.

Example 2 60 g. (0.225 mol) of pentachlorophenol and 95.5 g. (0.224 mol) of triethanolamine tall oil monoester were mixed together, whereupon a homogeneous solution resulted accompanied by a rise in temperature. The mixture was heated to 100 C. for 30 minutes with stirring to complete the reaction. A quantitative yield of a dark viscous liquid was obtained.

Eabample 3 The materials obtained in the foregoing examples were evaluated for their rust inhibiting properties by employing them in 1% by weight concentration in a phenol-treated Mid-Conti- 'nent lubricating oil of 120 secondsviscosity (Saybolt) at 210 R, which was used as the crankcase oil. in a single cylinder air cooled aviation type engine of 5.7 H. P. at 2400 R. P. M. speed, manufactured by the Wisconsin Motor Corporation. The engine was operated on 91 grade aviation gasoline containing; cc. tetraethyl lead per After running the engine for eight hours with the test oil, the steel cylinder which had the same composition as the cylinders of a full scale airplane engine, such as a Pratt and Whitney R1340 engine, was removed from the engine and stored in a Tenney humidity cabinet in which the temperature was caused to vary between 72 and 90 F. and the relative humidity between 94% and 53% during each 24 hour period. Typical conditions-in a tropical climate were thus simulated. After five days storage the amount of rust developed was determined and recorded as the percent of the total cylinder barrel area rusted. For comparison, oils con taining the constituents of the amine salts separately were similarly tested as well as a sample of the base oil containing no additive and a sample containing pentaerythritol monooleate, a well I known rust inhibitor. The results of the foregoing engine rust tests are given in the followmg table:

Percent Cylinder Barrel Oil or Oil Blend Tested Area Rusted After Days Storage Base oil 35 Base oil+l% pentaerythritol monooleata. Base oil+l% pentachlorophenol 9 Base oil+l% C 9 amine mixture of Example 12. 5

Base oil+triethanolamine tall oil mon 0ester. Base oil+l% salt of Example 1 3. 5 I Base oil+l% salt of Example 2 l V 4 It will be noted from the above that the salts formed by the reaction of pentachlorophenol with the amines are considerably more efiective than either the pentachlorophenol or the amines when used separately in similar amounts.

. Example 4 The product of Example 1 was tested as to effectiveness in increasing the load bearing capacity of a base stock, by blending the same in 2% proportion by weight in a phenol extracted coastal oil of 45 second Saybolt at 210 F. and testing the resulting blend in a Shell Four-ball E. P. Tester, made by Precision Scientific Company, and in the Almen machine. For comparison, samples of the base stock alone and of the base stock containing a commercial ester type oiliness agent were similarly tested. The results are shown in the following table:

In addition to the materials to be added ac cording to the present invention, other agents may also be used such as dyes, pour depressors, heat thickened fatty oils, sulfurized fatty oils, organo-metallic compounds, metallic or other soaps, sludge dispersers, antioxidants, thickeners, viscosity index improvers, oiliness' agents, resins, rubber, olefin polymers, voltolized fats, voltolized mineral oils, and/or voltolized waxes, and colloidal solids such as graphite, etc. Solvents and assisting agents, such as esters, ketones, alcohols, aldehydes, halogenated or nitrated compounds, and the like may also be employed.

In addition to being employed in crankcase lubricants the additives of the present invention may also be used in extreme pressure lubricants, engine flushing oils, industrial oils, general machinery oils, process oils, rust preventive compo- .sitions, and greases.

What is claimed is:

1. A composition consisting essentially of a mineral lubricating oil containing dissolved therein 0.01 to 10% of an amine salt of pentachlorophenol, the amine portion of said salt con taining a total of not less than eight carbon atoms and is a member of the class consisting of aliphatic and cycloaliphatic amines.

2. A composition according to claim 1 in which the amine salt is derived from an aliphatic amine. I

3. A composition accordingto claim 2 in which the amine is essentially of 018' chain length.

4. A composition according to claim 3 in which the amine contains at least one double bond.

5. A composition according to claim 1 in which the amine salt is derived from a high molecular Weight aliphatic acid ester of triethanol amine.

-6. A composition consisting, essentially of a mineral lubricating oil containing dissolved therein 0.01-10% of an amine salt of pentachlorophenol, the amine portion of said salt being derived from the tall oil monoester of triethanol amine.

'7. A composition consisting essentially of a mineral lubricating oil containing dissolved therein 0.01l0% of an amine salt of pentachlorophenol, the amine portion of said salt being less than 8 carbon atoms.

8. A composition consisting essentially of 9. UNITED STATES PATENTS I mineral lubricating 011 containing dissolved N b D therein 0.01-10% of an amine salt of pentachlo- 3 2 Man 1 rophenol, the amine portion of said salt being 2382976 Aug 1945 derived from a primary aliphatic amine of about 5 2389110 Cook Nov. 1945 Cw-Cm chain length. T

, OTHER REFERENCES CHARLES WEISEL- Industrial and Engineering Chemistry, vol. 38,

. No.10,hl m dAed L References Cited in the tile of this patent 10 i jfigijf f 5 add 

1. A COMPOSITION CONSISTING ESSENTIALLY OF A MINERAL LUBRICATING OIL CONTAINING DISSOLVED THEREIN 0.01 TO 10% OF AN AMINE SALT OF PENTACHLOROPHENOL, THE AMINE PORTION OF SAID SALT CONTAINING A TOTAL OF NOT LESS THAN EIGHT CARBON ATOMS AND IS A MEMBER OF THE CLASS CONSISTING OF ALIPHATIC AND CYCLOALIPHATIC AMINES. 